1. Field of the Invention
This invention relates to corrosion resistant manganese alloys and more particularly to the manufacture of bimetals that utilize manganese alloys as the high thermal expansive metal.
2. Description of the Prior Art
Composite thermostat metals (bimetals) are made of metalurgically bonded layers of various metals, at least one of which having a relatively high coefficient of thermal expansion and at least one other metal having a relatively low coefficient of thermal expansion. When the thermostat metals are subjected to temperature changes, the differences in the thermal expansion of the several layer materials give rise to stresses that are relieved by a flexing of the bimetal. This flexing or bending is utilized in variously conventional ways to actuate controls or the like in response to a temperature change. The amount of flexing which occurs in the thermostat metal in response to a temperature change is referred to as the "flexivity" of the thermostat metal and the flexivity of a given thermostat metal depends upon the difference of the thermal expansion properties of the several metals of the composite thermostat metal. To achieve high flexivity, special metal alloys are employed which either have a relatively high or a relatively low coefficient of thermal expansion.
The present invention has as its object the utilization of manganese alloys as the component of the bimetal that has the high coefficient of thermal expansion. Two alloys of this sort that are commonly available on the market place are comprised of 72% manganese, 18% copper and 10% nickel (72/18/10) and 75% manganese, 10% copper and 15% nickel (75/10/15). In addition to the high coefficient of thermal expansion (14.7.times.10.sup.-6 and 15.7.times.10.sup.-6 respectively) these alloys also are desirable as the component of a thermostat bimetal since they have high electrical resistivity, both in excess of 1000 ohms/cir mil ft. High electrical resistivity is important when a thermal response of the bimetal to an electrical current is desired as, for example, in circuit breakers and other current limiting devices.
While the coefficient of thermal expansion and electrical resistivity make manganese alloys in many ways ideally suited for use as a thermostat metal, those alloys have not been widely used due to the high chemical reactivity of manganese. For example, as given in the literature, manganese is listed 37th in the group of 43 metals for its thermodynamic nobility (immunity) and 43rd out of 43 for its practical nobility (immunity and passifation).
Not only do manganese alloys rapidly corrode under ambient conditions in which any moisture is present but the surface oxide layers that form are not protective and, given sufficient time, the metal alloy will eventually degrade to a powdery mass.
The corrosion of the manganese alloy is not only destructive, but the oxide layer makes it difficult to unit the alloy surfaces to other components of thermostats as by using conventional soldering or spot welding techniques. To obtain good adhesion between the elements, the manganese surface must be cleaned from oxide deposits. For these reasons, one must accept the problems of special storage, handling and cleaning techniques if the desirable advantages of manganese alloys are to be enjoyed as thermostat metals.
In U.S. Pat. No. 3,838,986 a method is proposed in which the surface oxide layer of manganese alloys can be tolerated in welding the alloy as part of a bimetal to another element of a thermostat. This patent discloses placing a layer of tin over the manganese oxide surface of the thermostat metal which, during resistance welding to a metal component of the thermostat, will absorb expelled manganese oxide and avoid the formation of weld flash. This method is not entirely satisfactory as it adds to the cost and, for the protective metal to be effective, it must be of sufficiently heavy gauge to retain its integrity during bonding. Since protective metals such as tin do not have the high expansive and high resistive properties of the manganese alloy, protective metals such as tin, to the extent that they are used, detract from the properties of the bimetal.
It has also been proposed that the manganese alloy be protected by electroplating a protective metal over its surface. This has proved unsatisfactory since, due to the extreme chemical reactivity of the manganese, it is not practical in the present state of the art to adequately control the electroplating operation.
Attempts also have been made to deposit protective metals on the surface of the manganese alloy by autocatylitc methods in which the surface deposition of a protective metal is obtained by immersing the alloy in a solution of a metal salt and a reducing agent. This process also has proven difficult to control again due to the extreme chemical reactivity of the manganese alloy.
Accordingly, it is an object of this invention to protect manganese alloys from corrosion.
Another object of this invention is to protect the surfaces of manganese alloys from corrosion so that they will be practical for use as thermostat metals.
These and other objects of this invention are achieved by directly replacing the manganese in the outermost surface layer of the alloy with a more noble metal, such as nickel, by intrinsic voltaic couple deposition. In this process, a direct electrochemical reaction takes place between the manganese metal and a metal ion to cause a replacement of the surface layer of manganese with the metal of the solution. For example the reaction of manganese with a nickel solution is EQU Mn+Ni.sup.++ (solution).fwdarw.Ni+Mn.sup.++ (solution)
The electric potentials are:
______________________________________ Mn = Mn.sup.++ + 2e.sup.- +1.18 Ni = Ni.sup.++ + 2e.sup.- +0.25 ______________________________________
E.degree. for the Mn:Ni.sup.++ couple is +0.93 indicating that the reaction is strongly favored. Control over the process is not particularly critical since the reaction will proceed only until the surface layer of manganese has been depleted and then the reaction will stop. This results in a protective coating that perhaps is only about 0.1 microns thick but this is sufficient to protect the alloy from chemical degradation and provide a shiny, oxide free surface to which other metals readily can be attached as by resistance welding or soldering.